Method for decreasing the drying time of a coating composition

Abstract: A method for decreasing the drying time of a wet coating by admixing said wet coating and a predetermined amount of at least one transient colorant, applying the admixture to a substrate, and causing or allowing the coating to dry. The transient colorant may be, for example, a pH-sensitive colorant or a photobleaching colorant.

Description: This invention relates to decreasing the drying time of an aqueous coating. Coating compositions may be applied to many structures. Aqueous and nonaqueous coating compositions must dry before the protective and aesthetic properties of the compositions can be fully achieved. The drying time of the coating composition is particularly important for aqueous coatings dried outside as the drying rate is adversely affected by high humidity and, at the same time, rain, or even heavy dew, may cause a catastrophic failure such as washout of the coating film. The problems of achieving quick drying for aqueous compositions are aggravated when the composition is low in solids content or is applied as a thick coating. The drying time of a coating composition depends on its temperature; colored coatings drying outdoors with incident sunlight may achieve a higher temperature and higher drying rate than white coatings owing to the greater absorption of radiative energy by a colored coating. Unfortunately, in many cases a colored coating is undesirable or unacceptable for functional and/or for aesthetic reasons. For example, white coatings are known to significantly reduce the surface temperature of roofs relative to dark colors. This reduction in surface temperature, which may be as much as 45 °C, may drastically lower the energy requre-ments for air conditioning and may lessen the thermal shock associated with rain striking a hot roof. Such roof coatings are typically fairly thick - a dried coating thickness of 30 to 40 mils is common - and drying may be slow. Slow drying may hamper the application of subsequent coatings, particularly in the case of thick coatings on roofs where it is necessary for an operative to walk on the first coating during the application of the second coating. Australian Patent AU 49046/72 discloses a surface coating composition incorporating a colouring substance which may be faded or leached out of the paint within a relatively short time. Expressly disclosed is a modified white or pastel coloured paint which is difficult to apply uniformly to a surface which has been precoated with a paint of the same colour. EP-A-0488980 discloses a wet hiding power developing system which does not alter the dry hiding power in a paint composition, which has a dry hiding power higher than the wet hiding power. The problem faced by the inventors was increasing the drying rate of an applied coating composition without permanently altering its appearance. According to a first aspect of the present invention there is provided use of a predetermined amount of at least one transient colorant in a wet coating applied to a substrate at a wet thickness greater than 10 mils for decreasing the drying time of a wet coating. The wet coating is preferably a wet mastic. The transient colorant is selected to provide a visible color to the wet coating, and thereby decrease the drying time of the wet coating when exposed to incident light, but to contribute, at most, a minimal level of color to the dried coating. The wet coating may be any pigmented or unpigmented architectural or industrial coating. The wet pigmented coating contains at least one pigment and at least one polymeric binder. The pigment may include inorganic materials such as, for example, titanium dioxide, calcium carbonate and clay, as well as organic pigments such as, for example, polystyrene beads and aqueous dispersions of water-insoluble polymers which yield air-filled voids on drying of the coating composition. The polymeric binder may include polymers such as, for example, acrylic (co)polymer, vinyl acetate polymer, vinyl/acrylic copolymer, styrene/acrylic copolymer, polyurethanes, styrene/bufadiene polymer, and mixtures thereof. Preferred are coatings wherein the polymeric binder is an aqueous emulsion addition polymer. Preferred are coatings applied in wet thicknesses of greater than 10 mils; especially preferred are coatings, mastics, caulks, and sealants which are applied in wet thicknesses greater than 20 mils, and which particularly benefit from faster drying. The coating may contain, in addition, other components such as, for example, emulsifiers, dispersants, curing agents, coalescents, wetting agents, biocides, thickeners, rheology modifiers, plasticizers, anti-foaming agents, and other colorants, waxes, or anti-oxidants. A transient colorant as defined herein is a composition such as, for example, a dye which substantially changes in color during or after the drying of a coating containing the transient colorant. The transient colorant in the wet coating is present in an amount effective to increase the drying rate of the coating relative to the drying rate of the coating absent the transient colorant. The transient colorant in the dry coating may contribute other beneficial properties in the dry film but must contribute, at most, a minimal level of color to the dry film after a period of drying such as, for example, one week. Preferred is an transient colorant which is strongly visible light-absorptive, i.e., deeply colored, in the wet coating and which is colorless or white in the-dry coating. The transient colorant is used at a level from 0.001 % to 0.5 %, by weight based on the weight of the wet coating. Preferred is a level from 0.03 % to 0.3 %, by weight based on the weight of the wet coating. Suitable transient colorants useful in the invention must substantially diminish in effectiveness in contributing to the absorption of visible light, or to the production of color, during or after the drying of a paint film containing the transient colorant. The agent causing the diminution of the light absorption may be external to the paint film or within the film. An external agent may be present in the ambient atmosphere or on the substrate surface, whether naturally occurring or externally introduced. External agents include, for example, oxygen, carbon dioxide, sulfur oxides, water (in the case of solvent-borne paints), salts and lignins. Agents within the film may result from a change in the composition of the film occasioned by the drying process itself such as, for example, a pH change or a change in the relative concentration of a complexation agent. The mechanism by which the transient colorant substantially diminishes in its effectiveness in contributing to light absorption, or color, during the drying of a paint film containing the transient colorant is not a limitation of this invention but may incdude mechanisms such as, for example, oxidation, dehydration, photobleaching, pH indicator effect, complexation and chemical reaction. Examples of suitable transient colorants include, for example, phenolphthalein, thymolphthalein, cresol red, o-cresolphthalein, fluorescein, aniline blue, rhodamine B, Janus green B, Toluidine Blue O, methylene blue, Evans blue, Safranin O, rose bengal, ruthenium red pararosaniline, and mixtures thereof. In one preferred embodiment of this invention an aqueous coating is admixed with at least one pH indicator which substantially decreases in color upon a change in paint pH occasioned by the drying of the coating. The intrinsic pH of a coating herein is taken to be the pH of the wet coating absent a volatile acid or base. If a wet coating, either during the preparation of the coating or thereafter, has been adjusted to a pH higher than its intrinsic pH at least in part with a volatile base such as, for example, ammonia, the pH of the wet coating will drop, i.e., the coating will become relatively more acidic, during the drying of the paint film and a pH-sensitive colorant, or indicator, which is colored at a pH higher than the intrinsic pH of the wet coating and which is substantially less colored or colorless at the intrinsic pH of the wet coating may be used. Alternatively, if a wet coating, either during the preparation of the coating or thereafter, has been adjusted to a pH lower than its intrinsic pH at least in part with a volatile acid such as, for example, acetic acid, the pH of the wet coating will increase, i.e., the coating will become relatively more basic, during the drying of the paint film and a pH-sensitive colorant, or indicator, which is colored at a pH lower than the intrinsic pH of the wet coating and which is substantially less colored or colorless at the intrinsic pH of the wet coating may be used. Suitable pH-sensitive colorants which are used with volatile bases include, for example, phenolphthalein, thymolphthalein, cresol red, o-cresol-phthalein, fluorescein, aniline blue, and mixtures therof. In another preferred embodiment of this invention an aqueous coating is admixed with at least one transient colorant which substantially decreases in color upon drying of the coating in air, the color change believed to be due to photobleaching of the colorant. Suitable colorants include phenolphthalein, thymolphthalein, cresol red, o-cresolphthalein, fluorescein, aniline blue, rhodamine B, Janus green B, Toluidine Blue O, methylene blue, Evans blue, Safranin O, rose bengal, ruthenium red, pararosaniline and mixtures thereof. The method of this invention for improving the drying time of a coating involves admixing a wet coating and at least one transient colorant, and applying the admixture to a substrate. The transient colorant may be dissolved or dispersed in the continuous phase of the paint. For example, when an aqueous or waterborne paint is used, the transient colorant may first be dissolved or dispersed in water or at least one water-miscible solvent, or mixtures thereof. A water-soluble dye is preferred. Admixing is easily accomplished with stirring or mechanical mixing. The substrate to which the admixture of this invention may be applied includes wood, plastic, metal, cementitious and asphaltic substrates and previously primed or coated substrates. Preferred substrates are architectural substrates such as walls, roofs, roofing membranes, windows, window frames and joints at the intersection of such substrates. The admixtures of this invention may be applied to a substrate by methods well known in the art of applying coatings, mastics, caulks, and sealants such as air-assisted spray, airless spray, brush, roller, mop, squeege and caulk gun. The following examples are intended to illustrate the method for increasing the drying rate of a coating of this invention. EXAMPLES 1-4 AND COMPARATIVE EXAMPLES A-B. Decreasing drying time of mastic coating with transient colorants. Preparation of Comparative A. The following ingredients were dispersed for 15 minutes at high speed in a Cowles mixer. Quantities given are in grams. Water 152.5 Ethylene glycol 24.4 Hydroxyethyl cellulose 4.2 (NATROSOL 250 MHR) Polyacid pigment dispersant (30% solids) 4.8 (TAMOL 850) Defoamer 1.9 (NOPCO NXZ) Titanium dioxide 70.4 (TI-PURE R-960) Zinc Oxide 46.9 (KADOX 915) Alumina 377.0 (ALCOA C-330) Biocide 2.1 (SKANE M-8) To the above grind were added the following, in the order given, with stirring: Acrylic polymeric binder (55% solids) 470.6 (RHOPLEX EC-1791) Coalescent 7.0 (TEXANOL) Defoamer 1.9 (NOPCO NXZ) NATROSOL is a trademark of Hercules Co.; TAMOL, SKANE, and RHOPLEX are trademarks of Rohm and Haas Co.; TI-PURE is a trademark of E.I. DuPont de Nemours Co.; KADOX is a trademark of Zinc Corporation of America ; ALCOA is a trademark of Aluminum Company of America; TEXANOL is a trademark of Eastman Kodak Co.; NOPCO is a trademark of Henkel Corp.. For Examples 1-3, 4.0 grams of colorant was dissolved in 20 grams of 3A (denatured) ethanol and the solution was diluted with 20 grams of water. To 1165 grams of Comparative A was added 10.0 grams of the colorant solution. For Example 4, 4.0 grams of phenolphthalein was added to 100 grams of 3A ethanol. To 1165 grams of Comparative A was added 11.0 grams of the colorant solution. For Comparative B. To 1165 grams of Comparative A was added 2.0 grams of lamp black dispersion (Colortrend 888-9907 colorant). Test films were cast using a 0.127 cm (50 mil) drawdown block, which yielded a dry coating of approximately 0.0508 cm (20 mils). The coated panels were placed outside on a horizontal plywood sheet at Springhouse, Pennsylvania on a sunny day with no clouds with the temperature at 28.6 °C (82°F) and the Relative Humidity at 40%. Films were checked every 5 minutes in determining the progression of drying. Skin formation time was the visual observation of a skin by light finger pressure. Tack-free time was based on touching the film with light finger pressure. Surface dry time was based on a thumb twist with moderate pressure to determine that there was a tough skin with an underlying soft layer. Total dry time was determined as the time to no coating movement under moderate pressure thumb twist. Results are reported in Table 1.1 Drying time (minutes) with transient colorant EXAMPLE Comp. A Comp. B 1 Added Colorant None Lamp Black Aniline Blue Initial Color white gray blue Skin Formation Time 50 20 25 Tack Free Time 60 25 30 Surface Dry Time 80 45 35 Total Dry Time 110 55 70 % Improvement --- 200 157 Final Color white gray white EXAMPLE 2 3 4 Added Colorant Janus Green B Toluidine Blue Phenolphthalein Initial Color purple-gray purple dark pink Skin Formation Time 15 15 25 Tack Free Time 20 20 30 Surface Dry Time 25 25 45 Total Dry Time 50 50 60 % Improvement 220 220 183 Final Color white white white Examples 1-4 of this invention demonstrate decreased drying time relative to Comparative A which contains no transient colorant. Decreased drying time is demonstrated for Comparative B containing a permanent colorant relative to Comparative A, but the appearance of the dried coating is permanently altered. EXAMPLES 5-9 AND COMPARATIVE EXAMPLES C-D. Decreasing drying time of mastic coatings with transient colorants. Comparative C was prepared in the same manner as Comparative A hereinabove. For Example 5, 12.0 grams of Phenol Red was was added with mixing to 1165 grams of Comparative A. For Example 6, 1.5 grams of 0-Cresolphthalein was dissolved in 100 grams of 3A (denatured) ethanol. To 1165 grams of Comparative A was added 6.5 grams of the colorant solution. For Example 7, 4.0 grams of Thymolphthalein was dissolved in 100 grams of 3A (denatured) ethanol. To 1165 grams of Comparative A was added 16.0 grams of the colorant solution. For Example 8, 4.0 grams of phenolphthalein was added to 100 grams of 3A ethanol. To 1165 grams of Comparative A was added 11.0 grams of the colorant solution. For Example 9, 1.0 grams of Toluidene Blue was dissolved in 50 grams of water. To 1165 grams of Comparative A was added 20.0 grams of the colorant solution. For Comparative D. To 1165 grams of Comparative A was added 2.0 grams of lamp black dispersion (Colortrend 888-9907 colorant). Test methods used were those presented above in Examples 1-4. The coated panels were placed outside on a horizontal plywood sheet at Springhouse, Pennsylvania on a sunny to partly cloudy day with the temperature at 21°C (70 °F) and the Relative Humidity at 30%. Results are reported in Table 5.1 Drying time with transient colorants Example Comp. C Comp. D 5 Added Colorant None Lamp Black Phenol Red Initial Color white gray pink Skin Formation Time 48 15 20 Tack Free Time 60 20 35 Surface Dry Time 70 35 55 Total Dry Time 105 45 80 % Improvement -- 233 131 Final Color white gray white Example 6 7 Added Colorant 0-Cresolphthalein Thymolphthalein Initial Color purple Lt. Blue Skin Formation Time 10 10 Tack Free Time 20 20 Surface Dry Time 35 45 Total Dry Time 55 90 % Improvement 190 117 Final Color white white Example 8 7 Added Colorant Phenolphthalein Toluidene Blue Initial Color Dark pink Dark purple Skin Formation Time 15 15 Tack Free Time 20 20 Surface Dry Time 35 30 Total Dry Time 50 40 % Improvement 210 260 Final Color white white Examples 5-9 of this invention demonstrate decreased drying time relative to Comparative C which contains no transient colorant. Decreased drying time is demonstrated for Comparative D containing a permanent colorant relative to Comparative C, but the appearance of the dried coating is permanently altered. EXAMPLES 10-11. Decreasing drying time of mastic coatings with transient colorants. Comparative E was prepared in the same manner as Comparative A hereinabove. For Example 10, 800 p.p.m. toluidine blue, based on binder weight was added with mixing to Comparative E. For Example 11, 800 p.p.m. methylene blue, based on binder weight was added with mixing to Comparative E. Test methods used for measuring dry times were those presented above in Examples 1-4. Reflectance was measured using a Colorgard 45/0 Reflectometer; with a Leneta chart color control, reflectance over white=80 and black=1. The coated panels were placed outside on a horizontal plywood sheet at Springhouse, Pennsylvania on a sunny, clear day with a very slight breeze, with the initial temperature at 24°C (75 °F) and the Relative Humidity at 43%. Results are reported in Table 10.1 Drying time with transient colorants Example Comp. E 10 11 Added Colorant None toluidene blue methylene blue Initial Color white purple/blue dark blue Tack Free Time(min.) 40 17 18 Surface Dry Time(min.) 60 30 25 Total Dry Time(min.) 170 80 60 Reflectance 1 hr. 94 77 64 2 hr. 94 70 81 3 day 92 88 83 5 day 91 87 85 7 day 90 86 90 Examples 10 and 11 of this invention exhibit decreased drying time relative to Comparative E. The color of Examples 10 and 11 faded to white over a 7 day period based on the reflectance data. EXAMPLES 12-13. Decreased drying time for dear caulk Preparation of Comparative F. The following ingredients were mixed for 45 minutes and then de-aerated. Acrylic latex (62% total solids) 726. 0 (Rhoplex 2620) Premix of: Water 8.0 Sodium lauryl sulfate (28%) 4.0 Biocide (KATHON LX (1.5%)) 0.6 Ethylene glycol 7.5 Propylene glycol 7.5 Premix of: Mineral oil 50.0 Silane Z-6040 Premix of: Water 40.0 Ammonium hydroxide (28%) 8.0 Biocide (SKANE M-8) 0.5 Silica (CAB-O-SIL M-5) 25.0 UV Stabilizer (TINUVIN 1130) 0.4 CAB-O-SIL is a trademark of the Cabot Corp.; TINUVIN is a trademark of Ciba-Geigy Corp. Preparation of Example 12. To 50 g. of Comparative F (clear caulk) was added 1.0 g. of a solution of 1.0 g. toluidine blue dissolved in 50 g. water. Preparation of Example 13. To 50 g. of Comparative E (clear caulk) was added 0.1 g. of a solution of 1.0 g. toluidine blue dissolved in 50 g. water. Caulks - Examples 12-13 and Comparative F- were cast in 3.5 inch diameter plastic Petri dishes to a thickness of 0.635 cm (0.25 inches) with a thermometer embedded in the caulk. Caulk samples were placed outside on a sunny day at 14°C (58°F) and Relative Humidity of 30%. Increased caulk temperature on exposure to sunlight for clear caulks incorporating transient colorant. Time Ambient Temp °C (°F.) Caulk Temperature °C (°F.) Comparative F Example 12 0 14.4 (58) 14.4 (58) 14.4 (58) 1 hr. 16.7 (62) 14.4 (58) 23.3 (74) 2 hr. 20.0 (68) 15.6 (60) 25.6 (78) After two weeks exposure, Example 13 was almost clear, almost colorless, and visibly less milky (i.e., drier) than Comparative F (which has a milky emulsion appearance when wet). After four weeks exposure, Example 13 was clear and colorless while Comparative F still appears milky white. Example 12 was still not colorless. Example 12 of this invention attains a higher temperature during drying, and, therefore, is believed to dry faster, than Comparative F. Example 13 of this invention dries faster than Comparative F and its transient color disappears on exposure. EXAMPLES 14-15. Decreasing drying time for Exterior Insulated Finish System (EIFS) Finish coat Preparation of Comparative G. EIFS Finish coat was prepared by mixing the following for minutes using a ribbon mixer (quantities are in grams). Acrylic latex (46.5% solids) 405.0 Ethylene glycol 5.0 Defoamer 2.0 (Nopco NXZ) Titanium dioxide 65.0 (TI-PURE R-942 Slurry) Quartz 1000.0 (MYSTIC WHITE #15)-150.0 (MYSTIC WHITE #90)-850.0 Attapulgite clay 10.0 (ATTAGEL 50) Biocides 6.0 (DOWCIL-75)-4.0 (SKANE M-8)-2.0 Coalescent 6.0 (TEXANOL) Anionic thickener 6.0 (RHOPLEX ASE-60) Water 18.03 Aqueous ammonia (28%) 2.0 MYSTIC WHITE is a trademark of U.S. Silica Co.; ATTAFEL is a trademark of Engelhard Corp. Preparation of Example 14. To 1165 grams of Comparative G was added, with stirring, 20.0 grams of a solution of 1.0 g. toluidine blue dissolved in 50 g. water. Preparation of Example 15. To 1165 grams of Comparative G was added, with stirring, 11.0 grams of a solution of 4.0 g. phenolphthalein dissolved in 100 g. denatured(3A) ethanol. Examples 14, 15, and Comparative G were cast on glass plates at a wet thickness of 0.3175 cm (0.125 inches) and were placed outside on a sunny, windy(ca. 10 m.p.h.) day with ambient temperature of 17°C (62° F) and 35% relative humidity. Drying rate data according to the test procedures of Example 1 are presented in Table 14.1. Drying of EIFS Finish coat Sample Comparative G Example 14 Example 15 Color white blue pink Skin Form. time 20 15 20 Tack Free time 30 30 30 Surface Dry time 120 60 120 Total Dry time 280 120 270 Example 14 of this invention exhibits a significantly decreased dry time relative to Comparative G. Example 15 is barely sufficient in amount of transient colorant to exhibit a decreased dry time in this use under these drying conditions. EXAMPLES 16-17. Decreasing dry time for elastomeric wall coating Preparation of elastomeric wall coating - Comparative H. The following ingredients (all quantities are in grams) were added in the order given and dispersed using a Cowles mixer at high speed for 15 minutes. Water 171.7 Anionic pigment dispersant(30% solids) 5.0 (TAMOL 850) Potassium tripolyphosphate 1.5 Defoamer 2.0 (NOPCO NXZ) Calcium carbonate 445.0 (CAMEL WITE) Titanium dioxide 74.2 (TI-PURE R-960) Zinc oxide 49.5 (KADOX 515) The following ingredients were added to the grind with stirring. Acrylic latex binder polymer 439.9 (RHOPLEX 2447) Defoamer 2.0 (NOPCO NXZ) Coalescent 7.3 (TEXANOL) Biocide 2.2 (SKANE M-8) Ammonia (28%) 1.0 Premix of: Ethylene glycol 25.7 Thickener (NATROSOL 250MXR) 4.4 Preparation of Example 16. To 1165 grams of Comparative H was added, with stirring, 20.0 grams of a solution of 1.0 g. toluidine blue dissolved in 50 g. water. Preparation of Example 17. To 1165 grams of Comparative H was added, with stirring, 11.0 grams of a solution of 4.0 g. phenolphthalein dissolved in 100 g. denatured (3A) ethanol. Examples 16, 17, and Comparative H were cast on glass plates at a wet thickness of 50 mils and were placed outside on a sunny, windy(ca. 10 m.p.h.) day with ambient temperature of 17°C (62° F) and 35% relative humidity. Drying rate data according to the test procedures of Example 1 are presented in Table 16.1. Drying of elastomeric wall coating Sample Comparative H Example 16 Example 17 Color white blue pink Skin Form. time 25 15 15 Tack Free time 55 25 30 Surface Dry time 80 50 60 Total Dry time 180 120 180 Example 16 of this invention exhibits a significantly decreased dry time relative to Comparative H. Example 17 is barely sufficient in amount of transient colorant to exhibit a decreased dry time in this use under these drying conditions. EXAMPLES 18-20. Decreasing drying time of a mastic coating on a hazy overcast day Comparative I was prepared in the same manner as Comparative A herein-above. For Example 18, 200 p.p.m. toluidine blue, based on binder weight was added with mixing to Comparative I. For Example 19, 400 p.p.m. toluidine blue, based on binder weight was added with mixing to Comparative I. For Example 20, 800 p.p.m. toluidine blue, based on binder weight was added with mixing to Comparative I. Test methods used for measuring dry times were those presented above in Examples 1-4. The coated panels were placed outside on a horizontal plywood sheet at Springhouse, Pennsylvania on a hazy, overcast day with approximately 75% cloud cover, with the temperature fluctuating between 21 -34°C (72-93° F) and the Relative Humidity fluctuating between 30-55%. Results are reported in Table 18.1 Drying time with transient colorants EXAMPLE Comp. I 18 19 20 Initial Color Tack Free white lt.blue med.blue blue/purple Time(min.) Surface Dry 40 25 20 15 Time(min.) Total Dry 120 50 50 35 Time(min.) 190 120 120 90 Examples 18-20 of this invention exhibit decreased drying time relative to Comparative I, even under hazy, overcast weather conditions.

Claims: Use of a predetermined amount of at least one transient colorant for the manufacture of a wet coating applied to a substrate at a wet thickness greater than 0.25 mm (10 mils) for decreasing the drying time of the wet coating. The use of claim 1, wherein the wet coating is a wet mastic. The use of claims 1 or 2 wherein said amount of said transient colorant is from 0.001% to 0.5%, preferably from 0.03% to 0.3%, by weight based on the weight of said wet coating. The use of claims 1, 2, or 3, wherein said transient colorant is selected from the group consisting of phenolphthalein, thymolphthalein, cresol red, o-cresolphthalein, fluorescein, aniline blue, toluidine blue, rhodamine B, Janus green B, Toluidine Blue O, Evans blue, Safranin O, rose bengal, methylene blue, ruthenium red, pararosaniline, and mixtures thereof. The use of any one of the preceding claims, wherein said coating in the wet state has a pH different from its intrinsic pH and is adapted to change in pH on drying, and wherein said transient colorant is a pH-sensitive colorant. The use of any one of claims 1-4, wherein said coating in the wet state has a pH higher than its intrinsic pH and is adapted to decrease in pH on drying and wherein said transient colorant is a pH-sensitive colorant. The use of any one of the preceding claims, wherein said transient colorant is a photobleaching colorant. The use of any one of the preceding claims, wherein said substrate is an architectural substrate.

Inventors: DETRICK GEORGE FRANK, FRANKEL LAWRENCE STEPHEN, GOMMEL ERNEST ROBERT, KIRN WILLIAM AUGUST, DETRICK, GEORGE FRANK, FRANKEL, LAWRENCE STEPHEN, GOMMEL, ERNEST ROBERT, KIRN, WILLIAM AUGUST
Applicants: ROHM & HAAS, ROHM AND HAAS COMPANY
Application year: 1994
Main classification: B05D7
IPC codes: C09D7, B05D3, B05D5, B05D7